Method of protectively treating and mounting photographic prints



July 2, 1957 E. H. LAND 2,798,021

METHOD OF PROTECTIVELY TREATING AND MOUNTING PHOTOGRAPHIC PRINTS Filed Sept. 25, 1953 2 Sheets-Sheet l July 2, 1957 D 2,798,021

PROTECTIVELY TREATING AND METHOD OF MOUNTING PHOTOGRAPHIC PRINTS Filed Sept. 25. 1953 2 Sheets-Sheet 2 ///1/ ///x///// ///ZA 1 1 1 7; 5

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United States Patent mini nor to Polaroid Min; corgorafiun ol' Delutinrporafvot\, (hunt; ridge, Mhss.,

w are Appieation September 25, 1953, Seria No. 382,301

14 Claims. (CL 154118) This invention relates to photography and more particularly to photographic methods of protectively treating and mounting photographic prints.

It has been previously proposed to provide photographic prints with protective coatings by applying to said prints a thin layer of a liquid composition containing a protective material in solution or in suspension. The protective material solidifies or coagulates to give on the surface 'of the print a thin, tough film. This approach, while essentially satisfactory, has some limitations in that it leaves an exposed tacky film on the surface of the print for as long as it takes the applied coating to dry and in that it requires a simple and effective disposable applicator and container for carrying enough of the composition to coat several prints,

It is accordingly one object of the present invention to provide a novel method of protectively treating and mounting photographic prints so as to largely overcome the above-noted limitation of applying a protective film as a part of a liquid coating, which method involves the simultaneous application of a fluid agent and the adhering of a preformed transparent protective sheet to the surface of a photographic print.

Another object of the invention is to provide a method of laminating a transparent protective sheet to the surface of a photographic print by a fluid agent, which method involves the application of the fluid to the print surface in a manner tending to wash from the surface of the print minute residues of reagents whose presence would otherwise tend to affect the stability of the print with time.

A further object is to provide a novel method of protectively treating-a photographic print whereby a transparent protective sheet is adhered to the print surface in a relatively simple and direct manner to produce a finished product which is pleasing in appearance and can be readily and simply mounted in an album or the like.

The invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description taken in connection with the accompanying drawings wherein:

Figure 1 is a somewhat diagrammatic perspective view, with parts broken away, of one form of photographic product illustrated, for clarity, with the elements separated and adapted to be employed in the method of the invention;

Fig. 2 is a view similar to Fig. l of another product adapted to be employed in the method of the present invention;

Fig. 3 is a sectional view of the product of Fig.1 illustrating a step in the method of the invention;

Fig. 4 is a view similar to Fig. 3 illustrating another Patented July 2, 1957 Fig 5 is a fragmentary sectional view of still another embodiment of a product metal in the method of the present invention; and

12 6 w a fr gmentary sectional view of u rumb 5 embodiment of a prmluct useful In the method of th present invention.

(Ilenerally. the herein disclosed invention is conc rncd with at. tofiiifit ifi startin 10 s ai d g iifif ghzre are discloscd novel phot r pl products for performing the method of the invention and adapted to be used individually with each print and a. plurality of these products may be provided as part of an assemblage furnished with each roll of film for protecting the several prints obtained from said roll. The novel method of the present invention is characterized by its simplicity and ease of performance whereby the above-mentioned products may be employed with a minimum of time, effort and equipment to provide protectively mounted photographic prints.

Referring now to the drawings, there is shown in Fig. 1 an assemblage 10 adapted to be employed in the method ofthe present invention. Assemblage 10 is illustrated as comprising a base sheet or support 12 and a transparent sheet 14 secured to the base sheet 12 by a hinge member 16.

Support 12 is generally rectangular, having a relatively large section 12a conforming to or larger than the photographic print to be mounted, and is adapted for mounting the entire processed assemblage, as for display purposes, in an album. End section 12b of support 12 may be providedwith means such as holes 120 adapted for mounting or securing'the processed assemblage in a photographic album. Support 12 may be formed of any suitable sheet material and may be substantially rigid for preventing bending or folding of the mounted photographic print or for mounting the assemblage.

Transparent sheet 14, adapted to provide a protective coating or surface for a finished photographic print, is so 40 mounted on support 12 by hinge member 16 as to permit the insertion of a photographic print, generally indicated at 18, between support 12 and sheet 14 in position to be laminated to sheet 14, and to permit access to the rear of print 18 after lamination with said sheet 14. Sheet 14 is generally rectangular and its dimensions may be equal to or greater than the photographic print laminated therewith. While the edges of sheet 14 have been illustrated as straight, they may be deckled to conform to the edges of a photographic print. Sheet 14 is formed of any suitable 0 transparent sheet material, and preferably of some suitable transparent plastic material, which may be laminated to a finished photographic print to form thereon a protective film substantially impervious to moisture and resistantto physical injuries. Examples of materials found 5 satisfactory for this purpose are: cellulose acetate, and particularly cellulose acetate sheet sold under the trade name Kodapak No. I, cellulose acetate with a subcoating comprised of polyvinyl alcohol and cellulose nitrate, cellulose tri-acetate sold under the trade name Kodapak No. IV, cellulose tri-acetate with a subcoating comprised of polyvinyl alcohol and cellulose nitrate, and cellulose acetate butyrate, sold under the trade name Kodapak No. II, with a suitable subcoat.

As a means for carrying a quantity of processing liquid adapted to laminate sheet 14 to print 18, there is provided a container 20 of the type disclosed in Patent No. 2,634,884, issued April 14, 1953, to Edwin H. Land for Collapsible Fluid Container, and in copending application Serial No. 74,791, filed February 5, 1949, by Edwin H. Land for Single Use Container Having a Sealed Passage; Adapted To Be UnsealedUpon Application of Stress.

sheet at least coextensive with said print and secured at one edge to a backing sheet, providing a quantity of said fluid in a rupturable container having an elongated discharge mouth and secured to one of said sheets between said sheets adjacent said one edgewith said discharge mouth directed away from said one end toward the opposite ends of said sheets, introducing said print between said sheets and an edge of saidprint between said backing sheet and a portion of said container comprising said discharge mouth whereby discharge of the fluid contents of said container between said print and said transparent sheet; is assured, superposing said transparent sheet with the image surface of said print, superposing said backing sheet with the opposite surface of said print, spreading said fluid from said container toward the opposite end of said print in a thin layer between said image surface and said transparent sheet whereby said image surface is treated by said fluid, the fluid being spread by applying compressive pressure to the sandwich comprising said sheets, print and container in superposition progressively, commencing at the end of said sandwich adjacent said container and progressing toward the opposite end of said sandwich, and retaining said transparent sheet in superposition with said image surface of said print so that said transparent sheet and print are caused to be laminated together as said fluid dries.

3. The method of claim 2 wherein said sheets are secured together by hinge means and said container is secured to the internal surfacetof said transparent sheet adjacent said hinge means with said discharge mouth extending substantially parallel with said hinge means.

4. The method of claim 2 wherein said container comprises a sheet of flexible transparent material folded upon itself and sealed at its edges to provide a fluid cavity and said discharge mouth.

. SL The method of claim 2 wherein said fluid is provided in a quantity in excess of that required for laminating said transparent sheet to said photographic print and is spread from said container at one end of the image surface of said print between the latter and said transparent sheet to the opposite. end of said image surface and from between said print and said transparent sheet, said excess fluid being trapped as it is spread from between said print and transparent sheet by at least a portion of said backing sheet located adjacent the end, of said transparent sheet opposite said rupturable container.

6. The method of claim 2 wherein said transparent sheet comprises an organic plastic material and said fluid includes at least a water solution of a hydrophilic polymer capable of bonding said transparent sheet to the image surface of said photographic print. a

7. The method of claim 2 wherein the discharge of the fluid contents of said container is effected by col? lapsing and compressing the walls of said container together.

6 8. The method of protectively treating a finished photographic print with a fluid and protectively mounting said print employing a photographic product comprising a generally rectangular preformed transparent sheet at least coextensive in area with said print and secured 65 along one edge by hinge means to a backing sheet, and an elongated rupturable container located between said sheets having discharge lips substantially coextensive with its length and substantially equal in length to the width of the image area of said print, said container 70 ing said print with said transparent sheet, said method 75 comprising the steps of introducing said photographic print between said sheets with one edge of said print located between the portion of said container comprising said discharge lips and said backing sheet with the image surface of said print facing said transparent sheet whereby discharge of said. fluid from said container between said transparent sheet and said image surface of said print is assured, superposing said transparent sheet with said image surface of said print, superposing the backing sheet with the rear surface, of said print, discharging said fluid from said container between said transparent sheet and one end of said print, spreading said fluid from adjacent said one end of said print between the image suriace of said print and said transparent sheet toward the opposite end of said print and said transparent sheet whereby treatment of said image surface is effected by said fluid, forming a thin film of said fluid between said image surface and said transparent sheet, and maintaining saidtransparent sheet and said print in superposition during drying of said film of fluid for laminating said transparent sheet with the image surface of said print.

9.; The method, of claim 8 wherein the treatment of said image surface of said print includes a washing action carried out bya wavefront of said fluid moved between said print and said transparent sheet from said one end ofsaid print adjacent said container toward said opposite end of said print by applying compressive pressure to said print and superposed sheets progressively from said one end toward said opposite end.

10, The method of claim 8 wherein the product employed to protectively treat and mount said print includes asupport strip secured between said backing sheet and said container for providing a slot between the portion of said container comprising said discharge lips and said sheet into which an end of said print is introduced, and wherein said end of said print is introduced into said space into abutment with said support strip for accurately locating said print relative to said sheets and said container. l

11. The method of claim 8 including the step, performed after lamination of said transparent sheet with said photographic print, of withdrawing the portion of said container comprising said discharge lips from be tween an edge portion of said print and said transparent sheet.

12. The method of claim 8 wherein said container of said photographic product, employed to protectively treat 0 and mount said print, comprises upper and lower walls and is secured at its lower wall to said backing sheet, and said transparent sheet is secured to said upper wall of said container.

13. The method of claim 8 wherein the container of the photographic product, employed for protectively treating and mounting said print, includes a fluid-filled cavity defined by upper and lower walls comprising an end section of said transparent sheet folded upon itself and secured to itself at its end and lateral margins, said 0 container being secured at its lower wall to said backing sheet and having a fluid-releasing passage, comprising the end margin of said transparent sheet and a portion of said transparent sheet secured thereto, capable of discharging the fluid contents of said container between said transparent sheet and a photographic print superposed with said transparent sheet with an end edge portion of said print located between said backing sheet and said end margin of said transparent sheet comprising said fluid-releasing passage.

14. The method of claim 8 wherein the discharge of said fluid from said container is accomplished by compressing and collapsing the walls of said container together.

(References on following page) References Cited in the file of this patent UNITED STATES PATENTS Gerber July 30, 1940 Peters May 2, 1944 5 Wolff June 7, 1949 Land Feb. 27, 1951 Land Sept. 2, 1952 Land Feb. 3, 1953 Land Sept. 29, 1953 10 10 FOREIGN PATENTS 567,011 Germany Dec. 24, 1932 456,471 Great Britain Mar. 10, 1936 OTHER REFERENCES Clerc: Photography: Theory and Practice, Pitman, New York, 2d ed., 1937, pp. 395-396. (Par. 615.)

Sttes Unite FUNGICIDE CONTAINING EUTADIENE-STY RENE CGPOLYMER Howard L. Yowell and Anthony H. Gleason, Westiield, N. 1., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Application March 24, 1953, Serial No. 344,459

3 Claims. (Cl. 1s7 4 2 their rapid loss in effectiveness when protective deposits of them on foliage surfaces are exposed to the weather. The parasiticides of this type are normally solid, but show a tendency to vaporize or sublime in the atmosphere and some may undergo chemical decomposition. Others are simply washed off by the action of rain. This is a 'particularly severe problem in the tropics where the rainfall is particularly heavy. It is, of course, important that chemical protectants for agricultural crops, when deposited on foliage, be resistant to washing off by rain since they are expected to give crop protection over extended periods when exposed to all kinds of weather. To improve this condition various wetting agents have been tried, such as bentonite, alcohol, acetone, tannic acid. Also a number of sticking agents have been tried, such as linseed oil, latex, and the like, without satisfactory results.

The problem of Weathering also occurs-with inorganic insecticide agents, of which lead arsenate is a common example. However, objectionable features of the inorganic agents, particularly dangers from poisoning of higher animal life before and during the time of their use, and their tendency toleave residues poisonous in this respect, makes it desirable to replace them bythe organic parasiticides which are not'toxic to higher animal life. However, to obtain full benefits from the organic parasiticides non-toxic to higher animal life, it is important that this kind of parasiticide be used in a composition with other ingredients which are likewise innocuous.

The primary purpose of this invention is to overcome previous drawbacks in the utilization of the organic parasiticides, with prolongation of potency and improvement of conditions under which these parasiticides are applied, and to adapt them for use with other ingredients to the best advantage, although it is not intended to exclude the use of the present invention with the inorganic parasiticides, since the improvements of the invention also apply to these materials.

Further objects of the present invention will become apparent from the following detailed description.

A particularly important type of parasiticide with which the sticker of this invention can profitably be used is the class of N-trichloromethylthioimides of dicarboxylic acids. The preparation of the latter is given in U. S. Patent No. 2,553,771, issued May 22, 1951, to A. R. Kittleson and H. L. Yowell. Typical of the N-trichloromethylthioimides of. dicarboxylic acids that can beused atent O "ice chloromethylthio phthalimide, N-trichloromethylthio succinimide, N-trichloromethylthio endomethylenetetrahydrophthalimide, and chlorinated N-trichloromethylthio tetrahydrophthalimide. N-trichloromethylthio tetrahydrophthalimide is especially effective and desirable.

Other parasiticides which can be used with the sticker of this invention include chlorinated insecticides, phosphate insecticides, inorganic insecticides such as lead arsenate, calcium arsenate, cryolite, etc. Fungicidesbactericides and germicides may also be applied in combination with this invention. These include such products as the thio carbonates, the imidazolines, chlorinated quinones, organic and inorganic copper salts such as copper naphthenate and bordeaux mixture, phenols, chlorinated phenols, quaternaries, etc. The elfectiveness of systemic and contact weed killers can also be improved by the use of the product described in this invention.

This invention is based on the discovery thatcertain liquid polymers and copolymers of butadiene andother diolefins have a remarkable ability to maintain-the described type of parasiticides in a uniform suspension, while acting as an adhesive for the particles and functioning effectively as a vaporization retardant to considerably reduce the loss of the insecticide. These polymers are obtained by polymerizing 65 to 100 parts of butadiene and 35 to 0 parts of styrene or its homologs either by batch or continuous process, by mass or emulsion polymerization.

The mass polymerization may bewith sodium-as a catalyst or with peroxide catalysts. Whensodium is used as the catalyst the polymerization is carried out in a reaction diluent at temperatures ranging from about 25 to 95 (1., preferably temperatures between 45 and. C., when a batch process is used and at 60 to (3., preferably 70-90 C., when a continuous process is used; As a polymerization catalyst about 1.2 to 8 parts of finely divided sodium per parts of monomers is used, preferably. 1.2. to 3 parts when a batch process is employed, and 2 to 5 parts when a continuous process is employed.

Materials used as diluents in the polymerization should be liquid at the polymerization temperature, that is, they should boil between 20 and 250 0., although more volatile'materials boiling as low as 15- C., may also be used, providing that the polymerization pressure is increased correspondingly. Preferred diluents are essentially aliphatic hydrocarbons such as naphtha (boiling range about 90 to C.) or straight run mineral spirits such as Varsol (boiling range about to 200 C.) but butane, pentane, benzene, toluene, xylene, cyclohexane, butenes, pentenes, or similar inert hydrocarbons are, also usable, individually or in admixture with each other. The hydrocarbon diluents are used in amounts ranging from 50 to 500 parts, preferably 100 to 400 parts per 100 parts by wt. of monomers in batch polymerizations, and 50 to 300 in continuous polymerization. The reaction can be promoted by the use of ethers as codiluents or modifiers along with the hydrocarbon diluent described above. A particular outstanding promoter for the batch process has been found in dioxane 1, 4, whose presence in the feed promotes the reaction sufficiently to give 100% conversion at 50 C., in a period of about 5-10 hours. Similarly favorable results were obtained with, the diethyl ether of ethylene glycol,

with diethyl ether (C2H5)20, and also with the diethyl ether of diethylene glycol,

In a batch process diethyl ether is usable, although the initial induction period tends to be somewhat. long. The diethyl ether of ethylene glycol is not preferred, be- 

1. THE METHOD OF TREATING A FINISHED PHOTOGRAPHIC PRINT WITH A FLUID AND PROTECTIVELY MOUNTING SAID PRINT, WHICH METHOD COMPRISES INTRODUCING SAID PHOTOGRAPHIC PRINT BETWEEN A PREFORMED TRANSPARENT SHEET AND A SUPPORT SHEET, BOTH OF WHICH ARE AT LEAST COEXTENSIVE WITH SAID PRINT, SUPERPOSING SAID TRANSPARENT SHEET WITH THE IMAGE SURFACE OF SAID PRINT WITH ONE EDGE OF SAID PRINT LOCATED ADJACENT THE RUPTURABLE MOUTH OF AN ELONGATED FLUID-FILLED CONTAINER, SAID SHEETS BEING SECURED TO ONE ANOTHER AT THE END OF SAID TRANSPARENT SHEET AND SAID CONTAINER BEING SECURED BETWEEN SAID SHEETS TO ONE OF SAID SHEETS ADJACENT SAID ONE END WITH SAID DISCHARGE MOUTH DIRECTED TOWARD SAID OTHER END OF SAID SHEETLS, SUPERPOSEING SAID SHEETS, CONTAINER AND PRINT AND APPLYING COMPRES SIVE PRESSURE THERETO PROGRESSIVELY, COMMENCING ADJACENT SAID ONE END TOWARD SAID OTHER END, WHEREBY SAID FLUIDD IS SPREAD FROM SAID CONTAINER TOWARD SAID OTHER END OF SAID SHEETS IN A THIN LAYER BETWEEN SAID PRINT AND SAID TRANSPARENT SHEET, PROTECTIVELY TREATING THE IMAGE SURFACE OF SAID PRINT WITH SAID FLUID, AND LAMINATING SAID TRANSPARENT SHEET WITH SAID PRINT. 